CN103383372B - To gather lead ion sensitive membrane and the Lead Ion-selective Electrode of sulfonation amino anthraquinones as carrier - Google Patents
To gather lead ion sensitive membrane and the Lead Ion-selective Electrode of sulfonation amino anthraquinones as carrier Download PDFInfo
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Abstract
The invention provides a kind of to contain amino, imido grpup and sulfonic poly-sulfonation amino anthraquinones as carrier is for surveying lead ion sensitive membrane and the Lead Ion-selective Electrode of trace lead ion concentration. The existing conventional film electrode of having reported relatively both at home and abroad, lead ion sensitive membrane provided by the present invention and Lead Ion-selective Electrode, it detects lower limit lower is 10-6.69Mol/L, the response time shorter is 16 seconds, be greater than 4 months service life. And the present invention uses oleic acid to replace ion-exchanger, without adding the ion-exchanger that is easy to be subject to illumination or Effect of Acidity On Absorption, has not only avoided being subject to the impact of illumination, acidity or mercury ion, has obtained good electrode performance simultaneously.
Description
Technical field
The invention belongs to analytical chemistry field, be specifically related to a kind of to contain amino, imido grpup and sulfonic poly-sulfonation ammoniaBase anthraquinone is that carrier is for surveying lead ion sensitive membrane and the Lead Ion-selective Electrode of trace lead ion concentration.
Background technology
Lead ion is ubiquity in natural environment, and has severe toxicity, will in the time that lead ion exceedes arm's length standard in human bodyNervous system on human body, immune system, brain tissue cause very large impact. At present, many analytical technologies can be used for lead ionContent analysis, as atomic absorption spectrography (AAS) (AAS), atomic fluorescence spectrometry (AFS), inductively coupled plasma mass spectrometry(ICP-MS) etc. But expensive instrument use and maintenance cost and special specialty operation can only rest on these methodsLaboratory. And based on ionophoric potentiometric sensor be a kind of rapidly and efficiently, analytical technology that cost is low, be particularly easy toBody carries and carries out outdoor operation, makes on-line monitoring become possibility.
For ion-selective electrode, the carrier embedding in sensing membrane is the core component that determines its performance, particularlyAspect ion-selective electrode anti-interference, ionophore is unique guarantee that ion-selective electrode obtains anti-interference. So farTill, for selective and Pb2+The carrier of coordination mainly contains crown ether (KazemiSY, the Shamsipur of suitable cavity sizeM,SharghiH.Lead-selectivepoly(vinylchloride)electrodesbasedonsomesynthesizedbenzo-substitutedmacrocyclicdiamides.JournalofHazardousMaterials, 2009,172 (1): 68-73), calixarenes macrocyclic compound (MichalskaA, WojciechowskiM,BulskaE,MaksymiukK.Experimentalstudyonstabilityofdifferentsolidcontactarrangementsofion-selectiveelectrodes.Talanta,2010,82(1):151-157)，And nitrogen-containing compound and some are rich in O, the large type organic of S equiatomic (GanjaliMR, Motakef-KazamiN,FaridbodF,KhoeeS,NorouziP.DeterminationofPb2+ionsbyamodifiedcarbonpasteelectrodebasedonmulti-walledcarbonnanotubes(MWCNTs)andNanosilica.JournalofHazardousMaterials, 2010,173 (1-3): 415-419) etc. But these yearsBody is synthetic loaded down with trivial details, thereby is difficult in actual applications promote. High-efficiency activated ionophoric shortage remains and hinders ion selectionThe biggest obstacle of electrode development.
In addition, at present for the conventional ion-exchanger of Lead Ion-selective Electrode mainly contain sodium tetraphenylborate (NaTPB),Four (4-fluorobenzene) Boratexes (NaTpFPB), four (4-fluorobenzene) potassium borates (KTpFPB), four (4-chlorobenzene) potassium borates (KTpClPB)And four [3,5-bis-(trifluoromethyl) phenyl] potassium borate (KTFPB), four [3,5-bis-(trifluoromethyl) phenyl] Boratex(NaTFPB) etc.,, because the phenyl ring on hydrogen proton meeting attack ion-exchange agent molecule causes degraded, therefore, electrode is at contact acidProperty is easy to after solution cause and detects the deteriorated of performance, and also has similar phenomenon when through long-time illumination, therefore electrode needs lucifugePreserve. Particularly normal and Pb2+The Hg coexisting2+Be easy to cause the boratory decomposition of tetraphenyl borate and four (4-chlorobenzene)(MurkovicI,WolfbeisOS.Fluorescence-basedsensormembraneformercury(II)Detection.SensorsandActuatorsB:Chemical1997,1997 (38-39): 246-251), and four [3,5-bis-(trifluoromethyl) phenyl] borate is more expensive again, therefore the octadecenic acid (OA) with plasticization substituted to tetraphenylboronHydrochlorate and four (4-chlorobenzene) borate provides new approaches for opening up without the lead ion sensitive membrane of conventional ion exchanger.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, provide a kind of to contain amino, imido grpup and sulfonic acidThe poly-sulfonation amino anthraquinones of base is that carrier is for surveying lead ion sensitive membrane and the Lead Ion-selective Electrode of trace lead ion concentration.
The present invention is used for surveying trace lead ion concentration to gather sulfonation amino anthraquinones (PSA) as potential response ionophoreSensing membrane and sensing electrode in carrier, PSA has stronger and complexing power lead ion, when it is selected as lead ionWhen electrode holder, imino group on its strand (NH-), carbonyl (C=O) and sulfonic group (SO3 -H+) to poly-sulfonation amino anthraceneThe conformation of quinone plays very important effect, is determining its pre-organized degree. What it can become a rigidity at space arrangement can notThe cavity of the approximate ring-type of polarization, lucky and Pb2+Size matches. Be suitable for lead ion as the pre-organized configuration of forming like this to bodyEnter and complexing, and then to Pb2+There is generation selective response.
Poly-sulfonation amino anthraquinones (PSA) described in the present invention is by chemical oxidization method, and sulfonation amino anthraquinones is carried outHomopolymerization, the fine powder obtaining. Owing to having introduced the merits such as amino, imino group, sulfonic group on condensed ring three cyclopolymer chain backbonesCan group, used as part, utilize its pre-organized effect, give it to the strong complexing of lead ion, make trace extremelyLead ion also can be made potential response.
One aspect of the present invention, first provides a kind of for surveying the lead ion sensitive membrane of trace lead ion concentration. Plumbous fromSub-sensitive membrane is the key components of ion-selective electrode, and its effect is that not only separately internal-filling liquid and two kinds of solution to be measured are moltenLiquid, produces selective response to certain electroactive material especially, forms film potential, and the key that produces this selective response existsIn membrane carrier. The present invention selects PSA as carrier, is because the sulfonation amino anthraquinones homopolymers being embedded in sensitive membrane can lead toAmino and the imino group isoreactivity point crossed on its strand carry out complexing Pb2+, form film potential, because the lead ion of testing sample is livedDegree is different, causes the lead ion activity difference of lead ion sensitive membrane surface complexation, and this also will cause the variation of film potential, and theyBetween meet nernst equation, therefore, can utilize nernst equation to infer in testing sample according to the film potential detectingLead ion activity. The concrete technical scheme adopting is as follows:
For surveying a lead ion sensitive membrane for trace lead ion concentration, it is characterized in that described lead ion sensitive membraneIn be dispersed with poly-sulfonation amino anthraquinones (, described lead ion sensitive membrane carried as potential response ion to gather sulfonation amino anthraquinonesBody), described poly-sulfonation amino anthraquinones is made by following methods:
1) transition metal salt is dissolved in the aqueous solution of perchloric acid;
2) monomer is dissolved in the water, preparation is containing the aqueous solution of monomer;
3) by step 1) and 2) gained solution blending polymerization reaction take place, obtain solubility oligomerisation sulfonation amino anthraquinones powderEnd;
Described monomer is the sulfonation amino anthraquinones with following general structure:
In formula, M is selected from H, NH4, Na or K.
Preferably, the structural formula of described monomer is as follows:
Preferably, described containing in the aqueous solution of perchloric acid, the molar concentration of perchloric acid is 10mmol/L-100mmol/L. ExcellentThe molar concentration of selecting perchloric acid is 30-50mmol/L, and the molar concentration of further optimizing perchloric acid is 50mmol/L.
Preferably, described transition metal salt is sodium chromate or potassium chromate.
Preferably, the mol ratio of described transition metal salt and monomer is 1:2-3:1.
Preferably, the temperature of described polymerisation is 0～50 DEG C.
Above-mentioned poly-sulfonation amino anthraquinones provided by the present invention is the in the situation that of not adding any stabilizing agent in the aqueous solutionAdopt synthetic the obtaining of method of chemical oxidising polymerisation. Reaction finish after, after filtration, washing (to remove byproduct of reaction, unreactedMonomer) obtain product after dry again.
Preferably, described poly-sulfonation amino anthraquinones is dispersed in described lead ion sensitive membrane with solid phase form.
Preferably, the content of described poly-sulfonation amino anthraquinones in lead ion sensitive membrane is 0.1～2.0wt%, is preferably1wt%。
Preferably, the raw material components of preparing described lead ion sensitive membrane comprises: (the poly-sulfonation of described potential response ionophoreAmino anthraquinones), host material, plasticizer and ion-exchanger.
Preferably, described potential response ionophore (poly-sulfonation amino anthraquinones), host material, plasticizer and ion-exchangeThe weight ratio of agent is 1:(30-60): (35-65): (0.5-2.0).
Preferably, described host material is selected from PVC, vinylite, polyacrylic acid, polyacrylate, silicon rubber and poly-Ammonia ester. Be preferably PVC.
Preferably, described plasticizer be selected from ortho-nitrophenyl octyl ether, Plexol 201, di-n-octyl phthalate,Dimethyl sebacate, dioctyl adipate, n-butyl phthalate or octadecenic acid. Preferably, described plasticizer is selected fromDi-n-octyl phthalate (DOP).
Preferably, described ion-exchanger is selected from sodium tetraphenylborate, tetraphenyl borate potassium, four (4-chlorobenzene) boronation potassium or 18Olefin(e) acid. Preferably, described ion-exchanger is octadecenic acid (OA).
The present invention also provides a kind of preparation method of above-mentioned lead ion sensitive membrane, comprises the steps: according to proportioning instituteState potential response ionophore (poly-sulfonation amino anthraquinones), host material, plasticizer and ion-exchanger and be dissolved in organic solvent,Film forming again after fully disperseing obtains described for surveying the lead ion sensitive membrane of trace lead ion concentration after solvent evaporates.
Wherein, described organic solvent is selected from oxolane, chloroform, carrene or acetone etc.
The invention also discloses the purposes of above-mentioned lead ion sensitive membrane, described lead ion sensitive membrane is for the preparation of liquidContact-type exploring electrode, Lead Ion-selective Electrode or for surveying the plumbum ion concentration of solution. Detectable plumbum ion concentrationBe 10-7mol/L～1.0×10-1mol/L。
The present invention on the other hand, also provides a kind of for surveying the Lead Ion-selective Electrode of trace lead ion concentration, withAbove-mentioned lead ion sensitive membrane is as the sensitive membrane of described Lead Ion-selective Electrode.
The formation of Lead Ion-selective Electrode described in the present invention can adopt the structure of existing ion-selective electrode, justThe above-mentioned lead ion sensitive membrane providing in the present invention is provided sensitive membrane wherein.
Preferably, the formation of the whole electrode of described Lead Ion-selective Electrode is: internal reference electrode | salt bridge | and interior reference is moltenLiquid lead ion sensitive membrane | solution to be measured | salt bridge | outer reference electrode.
Preferably, the internal reference electrode of described Lead Ion-selective Electrode is Ag/AgCl, and outer reference electrode is saturated calomel electricityThe utmost point.
Preferably, the interior reference solution of described Lead Ion-selective Electrode is that concentration is 10-5～10-4The nitric acid lead water of mol/LSolution, most preferably is 10-4The plumbi nitras aqueous solution of mol/L.
Preferably, the Alkitrate that described salt bridge is 1mol/L.
Most preferred, the formation of described whole electrode is: Ag/AgCl internal reference electrode | 1mol/L potassium nitrate salt bridge | and 10- 4The mol/L plumbi nitras aqueous solution | lead ion sensitive membrane | solution to be measured | 1mol/L potassium nitrate salt bridge | the outer reference electrode of SCE. WhereinSCE represents saturated calomel electrode.
Compared with the Lead Ion-selective Electrode of existing report, the lead ion taking sulfonation amino anthraquinones homopolymers as carrier is selectedThe advantage of electrode is:
(1) sulfonation amino anthraquinones homopolymers synthetic method is simple, and productive rate is high, and monomer source is abundant, and cost price is cheap.Be conducive to apply.
(2) reported existing conventional film electrode relatively both at home and abroad, it is lower that the present invention detects lower limit, is 10-6.69mol/L, and other conventional film electrodes are substantially 10-6Mol/L left and right; Response time of the present invention is shorter is 16 seconds, and other conventional filmElectrode is more than 20 seconds; Be greater than 4 months service life of the present invention; And the life-span one of doing Lead Ion-selective Electrode with other carrierAs be no more than 3 months.
(3) the existing conventional film electrode of having reported relatively both at home and abroad, the present invention is easy to be subject to illumination or acid without addingThe ion-exchanger, particularly some ion-exchangers of degree impact are easy to decompose in the solution that contains mercury ion, and the present inventionUse oleic acid to replace ion-exchanger not only to avoid being subject to the impact of illumination, acidity or mercury ion, obtained preferably simultaneouslyElectrode performance.
Brief description of the drawings
The potential response curve of the different DOP consumptions of Fig. 1 to lead ion;
The potential response curve of the different PSA carrier of Fig. 2 consumption to lead ion;
Potential response curve to lead ion after Fig. 3 OA substitutional ion exchanger;
Fig. 4 consists of the sensitive membrane of PSA:PVC:DOP:OA=1:33:61:5 to the response time of lead ion;
The sensitive membrane that Fig. 5 consists of PSA:PVC:DOP:OA=1:33:61:5 is 10 at plumbum ion concentration-4When mol/L, respondThe relation curve of current potential and pH value of solution;
Fig. 6 is with 1 × 10-3The EDTA solution titration 1 × 10 of mol/L-3mol/LPb(NO3)2The titration curve of solution;
Fig. 7 is with 1 × 10-3The EDTA solution titration 1 × 10 of mol/L-4mol/LPb(NO3)2The titration curve of solution.
Detailed description of the invention
Further set forth the present invention below in conjunction with embodiment. Should be understood that these embodiment are only for the present invention is described, but notLimit the scope of the invention.
Embodiment 1: gather the synthetic of sulfonation amino anthraquinones
Accurately take 1-amino anthraquinones-5-ichthyodin monomer (1.0g, 3.12mmol) and add 220mL distilled water, be placed in 25Strong stirring 30 minutes in DEG C water bath with thermostatic control. In addition by K2CrO4(1.22g, 6.24mmol) and 70%HClO4(1.07mL) dissolveIn the 29mL aqueous solution, be also placed in 25 DEG C of water bath with thermostatic control strong stirrings 30 minutes. Then by oxidizing agent solution with 3 seconds oneSpeed is added drop-wise in monomer solution, dropwises, 25 DEG C of lower magnetic force stirring reactions 72 hours. Reaction finishes to filter, and repeatedly usesWater, ethanol washing, to remove byproduct of reaction, unreacted monomer. Gained powder is placed at 50 DEG C and dries and within 3 days, obtain poly-sulphurChange amino anthraquinones, polymerization yield rate is 43.4%.
Embodiment 2: gather the synthetic of sulfonation amino anthraquinones
Accurately take 1-amino anthraquinones-5-ichthyodin monomer (2.0g, 6.24mmol) and add 300mL distilled water, be placed in 25Strong stirring 20 minutes in DEG C water bath with thermostatic control. In addition by K2CrO4(2.43g, 12.48mmol) is dissolved in the HClO of 50mmol/L4In the aqueous solution, be also placed in 25 DEG C of water bath with thermostatic control strong stirrings 20 minutes. Then monomer solution and oxidizing agent solution are mixed to 25DEG C lower magnetic force stirring reaction 72 hours. Reaction finishes to filter, and water, ethanol washing repeatedly, to remove byproduct of reaction, unreactedMonomer. Gained powder is placed at 50 DEG C and is dried 3 days, it is being dissolved in to organic solvent dimethyl sulfoxide (DMSO), get its solution 50At DEG C, dry 3 days and get final product. Synthetic yield is 21.7%.
Embodiment 3: gather the synthetic of sulfonation amino anthraquinones
Accurately take 1-amino anthraquinones-5-ichthyodin monomer (1.91g, 6.24mmol) and add 400mL distilled water, be placed in 25Strong stirring 20 minutes in DEG C water bath with thermostatic control. In addition by K2CrO4(3.64g, 18.72mmol) is dissolved in the HClO of 50mmol/L4In the aqueous solution, be also placed in 25 DEG C of water bath with thermostatic control strong stirrings 20 minutes. Then monomer solution and oxidizing agent solution are mixed to 25DEG C lower magnetic force stirring reaction 72 hours. Reaction finishes to filter, and water, ethanol washing repeatedly, to remove byproduct of reaction, unreactedMonomer. Gained powder is placed at 50 DEG C and is dried 3 days, it is being dissolved in to organic solvent methyl-sulfoxide, get its solution at 50 DEG CLower oven dry 3 days and get final product. Synthetic yield is 19.8%.
Embodiment 4: the assembling of lead ion electrode
Taking 300mg gross mass as benchmark, weighed PSA(3mg by 1:33:65:1 than row), PVC(99mg), DOP(195mg) and NaTPB(3mg) these four kinds of materials. PSA and NaTPB are joined in 5mL oxolane, simultaneously by PVC and DOPAlso join in 5mL oxolane, intermittently ultrasonicly impel it to disperse (disperseing more carefully better), then will contain PSA and NaTPBOxolane join in the oxolane containing PVC and DOP, constant temperature is stirred to and is sticky shape at 20 DEG C. Then mixed liquor is wateredCasting film forming on polyfluortetraethylene plate, after oxolane volatilizees completely, the PVC film that obtains containing potential response ion (plumbous fromSub-sensitive membrane), film thickness is in 150 μ m left and right.
Female film of above-mentioned preparation is taken off in water, then cut the disk that diameter is about 12mm, use modified acroleic acid fatSticking at internal diameter is the plastics pipe end that 10mm, external diameter are 12mm, after it is natural drying, contains 10 toward being filled with in pipe-4The Pb of M(NO3)2Solution 2mL, and insert Ag/AgCl reference electrode and do internal reference electrode. Electrode, before using for the first time, needs to use1.00×10-3The lead nitrate solution modulation 24h of mol/L.
The battery structure of measuring current potential is:
Ag/AgCl internal reference electrode | 1mol/L Alkitrate | 10-4The mol/L plumbi nitras aqueous solution | lead ion sensitivityFilm | solution to be measured | 1mol/L Alkitrate | Hg2Cl2The outer reference electrode of/Hg.
Test solution temperature: T=20.0 DEG C
Before test, measure first respectively the solution to be measured of 5～10 groups of known plumbum ion concentrations, according to measurement result, with electricityUtmost point response current potential is ordinate, with log[Pb (II), mol/L] be abscissa, wherein the concentration of lead ion is by debye-shockYour formula converts activity to, makes electrode response current potential and log[Pb (II), mol/L] relation curve.
The impact of embodiment 5:DOP consumption on Responsibility of the electrode
In the time investigating DOP consumption on the affecting of electrode performance, can adopt fixed potential response ionophore and ion to hand overChange the proportioning of agent, and the gross mass of sensitive membrane also remains unchanged, only regulate by the proportioning and the content that change PVC and DOP. ByResponse current potential in sensitive membrane is not only relevant with the kind of plasticizer, and also relevant with the content of plasticizer. Therefore the present inventionIn plasticizer be chosen as DOP, be because DOP is proved to be as the conducting polymer ion-selective electrode performance that is carrierThe most excellent plasticizer. By joining of fixing sensitive membrane gross mass and fixed potential response ionophore and ion-exchangerRatio, the potential response curve in four kinds of different PVC and DOP proportioning is shown in Fig. 1. In theory, too much plasticizer can cause that ion existsDiffusion coefficient in film becomes large and produced film ion current, thereby disturbs compared with the acquisition of low-detection lower limit, therefore reduces sensitive membranePlasticizer consumption in formula is also proposed, but from Fig. 1 and table 1, the consumption of plasticizer neither be fewer, propertyCan be better, if the consumption of plasticizer is host material 2 times time, detect lower limit minimum, reach 10-6.6Mol/L, this also meetsThe classics formula of conventional P VC film.
The performance of table 1. plasticizer consumption and Lead Ion-selective Electrode
The impact of embodiment 6:PSA carrier consumption on Responsibility of the electrode
In the time investigating carrier consumption on the affecting of electrode performance, the proportioning that can adopt fixed base material and plasticizer withAnd the consumption of ion-exchanger is constant, only regulate by the consumption that changes potential response ionophore PSA. Potential response ionCarrier is as determining ion-selective electrode sensitiveness and key factor optionally, and therefore the enough carriers in sensitive membrane are electrodesObtain the basic guarantee of this special response slope of energy. When carrier-free or carrier amount are very few, the response slope of electrode is well below theoryValue or basic non-responsiveness energy. Also can learn from Fig. 2 and table 2, in the time that the content of PSA in sensitive membrane is 0.5%wt, generationSlope only has 16.2mV/decade, well below nernst theory slope, only has in the time that vector contg is increased to 1.0%wt and just accords withClose this special response slope of energy, reached 29.5mV/decade. But, when the content that continues to increase PSA is to 1.5%wt and 2.0%wtTime, although can change not quite by this special response slope, detecting when lower limit is 1.0%wt compared with vector contg and increase, this mayThe defect that may cause sensitive membrane due to too high carrier consumption, because this carrier of PSA is at PVC film with solid phase dispersionIn, instead of be dissolved in plasticizer as conventional organic compound carrier, and in theory, carrier too much in sensing membrane willIncreased film ion current, be unfavorable for compared with the obtaining of low-detection lower limit, therefore, can this special response slope and lower inspection in order to obtainSurvey lower limit, increasing potential response ionophore consumption also should be careful.
The performance of table 2. carrier consumption and Lead Ion-selective Electrode
Embodiment 7:OA substitutional ion exchanger rear electrode response performance
Because hydrogen proton meeting attack conventional ion exchanger is as on tetraphenyl borate and four (4-chlorobenzene) borate moleculePhenyl ring and cause degraded, therefore, electrode is easy to cause and detects the deteriorated of performance after contact acid solution, and through long-timeElectrode when illumination, also has similar phenomenon, therefore need keep in Dark Place. Particularly normal and Pb2+The Hg coexisting2+Be easy to cause tetraphenyl borateWith four (4-chlorobenzene) boratory decomposition, and four [3,5-bis-(trifluoromethyl) phenyl] borate is more expensive again.
The octadecenic acid (OA) with plasticization is substituted sodium tetraphenylborate by the present invention, got rid of and used lipophilicity poorNaTPB, can fundamentally solve its leakage problem, thereby electrode performance is made moderate progress, as detected lower limit by 10- 6.55Mol/L has been reduced to 10-6.69Mol/L, and investigative range is by 10-6.0～10-2Mol/L has widened 10-6.3～10-1.6mol/L. However, also can find out from Fig. 3 and table 3, the content of OA in film can not be too high, because, too high can leakage and seriousThis special response of Recombinant Interferon α-2b, for example: when OA content is 10%wt and 20%wt, response slope only has 9.1mV/decade and 8.1mV/Decade, therefore, the optimized OA content of the present invention is 5%wt.
Table 3. is without the relation of OA consumption and electrode performance in the situation of conventional ion exchanger
Embodiment 8: the impact of internal-filling liquid plumbum ion concentration on Responsibility of the electrode
In order to reduce the detection lower limit of ion-selective electrode, a lot of methods are used to reduce even to eliminate in sensing membrane and existIon current, as reduce main ion in internal-filling liquid concentration, optimize carrier consumption, reduce ion-exchanger consumption, embed parentFat particulate, increase sensing membrane thickness, use rotation electrode, apply the serial of methods such as outside pole galvanic current. In the present invention justBy obtaining lower detection lower limit with the interior reference solution of variable concentrations, when the concentration of interior reference solution is 10- 5When mol/L lead ion, the detection lower limit of electrode is 10 compared with internal-filling liquid-4The decline of mol/L nearly 5 times, unique shortcoming is exactlyInterior reference solution is 10-5When mol/L, the less stable of electrode in low concentration lead liquid, is unfavorable for reading numerical values, therefore thisBrightly finally choose 10-4The plumbi nitras of mol/L is as optimized interior reference solution concentration.
Embodiment 9: the response time of electrode
Ion-selective electrode and reference electrode start or in liquid to be measured, lead that electrode is motionless from contact measured liquidThe ionic activity beginning that changes, reaches the required time of stable response while being called the response of ion-selective electrode to electrode potentialBetween. The present invention adopts in the motionless situation of electrode and changes the response time that in liquid to be measured, main ion activity is observed electrode. Institute surveysThe response time of the membrane electrode that the composition weight ratio obtaining is PSA:PVC:DOP:OA=1:33:61:5 is seen Fig. 4. Can find out,10-6Mol/L and 10-5The Pb of mol/L2+The time that concentration bottom electrode current potential reaches balance is about 22s, and along with plumbum ion concentrationIncrease, the response time is shorter and shorter, as 10-4Mol/L and 10-3The Pb of mol/L2+Concentration bottom electrode current potential reaches balanceTime only has 16s.
Embodiment 10:pH current potential platen window
In the time that the pH that investigates solution affects, can adopt the HNO of 0.1mol/L3PH value to solution regulates. ResponsiveThe response current potential of film is not only relevant with the ion concentration in solution, but also relevant with the pH value of solution. Sensitive membrane will obtain excellentGood result of use, require it to change pH blunt, that is pH flat roof area is wide. Be PSA:PVC for composition weight ratio:The membrane electrode of DOP:OA=1:33:61:5 is 10-4In the plumbous liquid of mol/L, the relation of potential response and pH value is shown in Fig. 5. Can find out,Within the scope of investigated pH, the electromotive force platform area that current potential does not change with pH is pH current potential platen window, and lower andWhen high pH, be all the oblique line with certain slope, current potential will be affected by pH, and therefore, pH current potential platen window of the present invention is 3.63～5.22。
Embodiment 11: electrode selective
Membrane electrode selectively refer to the selective response to corresponding ion under the condition existing at extraneous interfering ion, choosingSelecting property size has determined the accuracy of test result to a great extent, is the important parameter of weighing electrode antijamming capability. ThisInvention adopts the fixing interfering ion method in mixed solution method to study it and selects coefficient. Interfering ion concentration is fixed as 1.00 ×10-3Mol/L. The logarithm value of measured selection coefficient is listed in table 4. As can be seen from Table 4, for the interfering ion of+1 valencySelect coefficient logarithmAll be less than 1, and for the interfering ion of+divalent, except mercury ion, remaining interference coefficient logarithmAll be less than-2, this illustrates that the Lead Ion-selective Electrode taking PSA as carrier has well selective to lead ion. ButEvery kind of interfering ion also has very large difference to the annoyance level of lead ion, and the interference of 17 kinds of ions is arranged as from big to small:
+ 1 valency ion: Ag+>Na+>NH4 +>K+
+ divalent ion: Hg2+>Cd2+>Cu2+>Ba2+>Ca2+>Co2+>Zn2+>Mg2+>Mn2+>Ni2+
+ 3 valency ion: Cr3+>Al3+>Fe3+
Table 4. is fixed the selectivity factor of the measured lead ion sensitive membrane of interfering ion method
Embodiment 12: the service life of electrode
Table 5 is sensitive membrane of consisting of PSA:PVC:DOP:OA=1:33:61:5 in different service time to lead ionResponse performance, in front surrounding, carries out the test of calibration curve with semiweekly frequency, and after surrounding, with weeklyFrequency is tested. As an important indicator of ion-selective electrode, it is generally acknowledged when slope is lower than initial oblique service lifeRate 95% time, think this electrode failure. As known from Table 5, electrode slope of the present invention is higher than 95% of initial slope, electrodeAlso do not lose efficacy, therefore electrode life of the present invention has exceeded 16 weeks.
(thickness is 150 μ m, internal-filling liquid for the service time of the Lead Ion-selective Electrode that table 5. is carrier based on PSA and performanceBe 10-4mol/LPb(NO3)2)
Embodiment 13-14 titration indicator electrode
The membrane electrode that selective membrane composition weight ratio is PSA:PVC:DOP:OA=1:33:61:5, drips used as EDTA current potentialDetermine the indicator electrode of lead ion. With 1.00 × 10-3EDTA titration 20.00mL1.00 × 10 of mol/L-3Pb (the NO of mol/L3)2Standard liquid, as shown in Figure 6, the response current potential from Fig. 6 keeps starting steady state value can determine titration end-point to titration curve, thisShow that the lead ion selective membrane electrode taking PSA as carrier can be used for the indicator electrode of lead ion constant-current titration. Adopt same sample prescriptionMethod is with 1.00 × 10-3EDTA titration 20.00mL1.00 × 10 of mol/L-4Pb (the NO of mol/L3)2Standard liquid also hasSimilarly result, is shown in titration curve in Fig. 7.
Claims (4)
1. for surveying a lead ion sensitive membrane for trace lead ion concentration, it is characterized in that, prepare described lead ion sensitivityThe raw material components of film comprises: poly-sulfonation amino anthraquinones, host material, plasticizer and ion-exchanger; Described poly-sulfonation amino anthraceneThe weight ratio of quinone, host material, plasticizer and ion-exchanger is 1:(30-60): (35-65): (0.5-2.0); Described matrixMaterial is selected from PVC, vinylite, polyacrylic acid, polyacrylate, silicon rubber and polyurethane; Described plasticizer is selected from adjacent nitreBase benzene octyl ether, Plexol 201, di-n-octyl phthalate, dimethyl sebacate, dioctyl adipate, O-phthalicAcid di-n-butyl or octadecenic acid; Described ion-exchanger is octadecenic acid; Described poly-sulfonation amino anthraquinones is by following methods system:
1) transition metal salt is dissolved in the aqueous solution of perchloric acid;
2) monomer is dissolved in the water, preparation is containing the aqueous solution of monomer;
3) by step 1) and 2) gained solution blending polymerization reaction take place, solubility oligomerisation sulfonation amino anthraquinones powder obtained;
Described monomer is the sulfonation amino anthraquinones with following general structure:
In formula, M is selected from H, NH4, Na or K; The content of described poly-sulfonation amino anthraquinones in lead ion sensitive membrane is 0.1～2.0wt％；
In the aqueous solution of described perchloric acid, the molar concentration of perchloric acid is 10mmol/L-100mmol/L; Described transition metal saltFor sodium chromate or potassium chromate; The mol ratio of described transition metal salt and monomer is 1:2-3:1;
The temperature of described polymerisation is 0～50 DEG C;
Described poly-sulfonation amino anthraquinones is dispersed in described lead ion sensitive membrane with solid phase form.
2. for surveying a Lead Ion-selective Electrode for trace lead ion concentration, it is characterized in that, described lead ion is selected electricityThe sensitive membrane extremely going up is lead ion sensitive membrane as described in claim 1.
3. as claimed in claim 2 for surveying the Lead Ion-selective Electrode of trace lead ion concentration, it is characterized in that: described inThe formation of the whole electrode of Lead Ion-selective Electrode is: internal reference electrode | salt bridge | and interior reference solution | lead ion sensitive membrane | to be measuredSolution | salt bridge | outer reference electrode.
4. as claimed in claim 3ly it is characterized in that for surveying the Lead Ion-selective Electrode of trace lead ion concentration, described inInternal reference electrode is Ag/AgCl, and outer reference electrode is saturated calomel electrode; Described reference solution is that concentration is 10-5～10- 4The plumbi nitras aqueous solution of mol/L.
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| CN101215378A (en) * | 2007-12-28 | 2008-07-09 | 同济大学 | Polyamino anthraquinone sulfonic acids, synthesis method and use thereof |
| CN101308113A (en) * | 2008-01-23 | 2008-11-19 | 同济大学 | Lead ion selective electrode film using poly-1-aminoanthraquinone as carrier, its preparation method and uses thereof |
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| CN101215378A (en) * | 2007-12-28 | 2008-07-09 | 同济大学 | Polyamino anthraquinone sulfonic acids, synthesis method and use thereof |
| CN101308113A (en) * | 2008-01-23 | 2008-11-19 | 同济大学 | Lead ion selective electrode film using poly-1-aminoanthraquinone as carrier, its preparation method and uses thereof |
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| Title |
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| Facile Synthesis of Polysulfoaminoanthraquinone Nanosorbents for Rapid Removal and Ultrasensitive Fluorescent Detection of Heavy Metal Ions;Mei-Rong Huang等;《The Journal of Physical Chemistry C》;20110316;第115卷(第13期);第5302-5303页 * |
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